Polyester resins flame retarded by poly(metal phosphinate)s

Abstract

Polyesters, polyamides and polyester-polyamides are flame retarded by incorporating a flame retardant amount of selected poly(metal phosphinate)s with the resins. The poly(metal phosphinate)s can be incorporated with the resins either by admixture of the poly(metal phosphinate)s with the polyester or polyamide or by adding the poly(metal phosphinate)s to the polyester or polyamide polymerization reaction whereby the poly(metal phosphinate)s become a part of the polymer structure.

1.  The flame retarded resin compositions comprising a polyester and a flame retardant amount, namely 2.5 to 20 parts by weight per 100 parts by weight of polyester of at least one poly(metal phosphinate)s having one, two, three of four phosphinate groups per coordination center and selected from the respective formulae: (a) MX, MaX, Ma 2  X, Ma 3  X, M(AA)X, M(AA) 2  X,   (b) MX 2 , MaX 2 , Ma 2  X 2 , MabX 2 , M(AA)X 2 ,   (c) MX 3 , MaX 3 , Ma 2  X 3 , MabX 3 , M(AA)X 3 , or   (d) MX 4   wherein     M is a metal selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, titanium, zirconium, antimony, bismuth, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, cadmium, mercury, aluminum, tin, lead and mixtures thereof;   X is a disubstituted phosphinate group having the structure ##STR4##  wherein R and R 1  are independently selected from the group consisting of an aliphatic group of 1 to 20 carbons, a cycloaliphatic group of 3 to 20 carbons, an aromatic group of 6 to 12 carbons and said aliphatic, cycloaliphatic or aromatic groups can have substituted thereon, the substituted group being selected from the class consisting of a halogen, ether, hydroxyl, alkoxy, ketone and ester;   a and b are independent unidentate groups selected from the class consisting of oxy, alkoxy, hydroxyl and halide; and   AA is a bidentate ligand selected from the group consisting of acetylacetonate, picolinate, 8-hydroxyquinolinate, dimethylglyoximate and glycinate.   
     
     
       2. The flame retarded composition of claim 1 in which the poly(metal phosphinate) is Zn[(C 6  H 5 )(CH 3 )PO 2  ] 2 . 
     
     
       3. The flame retarded composition of claim 1 wherein M is selected from the group consisting of copper, iron, tin, cobalt, tungsten, manganese, chromium, vanadium, titanium, zinc, cadmium, molybdenum and the phosphinic acid ##STR5## used to make the poly(metal phosphinate)s is selected from the group consisting of dibutylphosphinic acid, dioctylphosphinic acid, diphenylphosphinic acid, methylphenylphosphinic acid and phenylhydroxmethylphosphinic acid, bis(hydroxymethyl)phosphinic acid, and bis(hydroxyethyl)phosphinic acid. 
     
     
       4. The flame retarded composition of claim 1 in which the polyester is poly(ethylene terephthalate) 
     
     
       5. The flame retardant composition of claim 1 wherein the poly(metal phosphinate) is zinc bix(hydroxymethyl)-phosphinate and the resin composition is poly(ethylene terephthalate). 
     
     
       6. A process of preparing flame retarded polyester resins comprising incorporating with the said resins a flame retardant amount, namely 2.5 to 20 parts by weight per 100 parts by weight of polyester of at least one poly(metal phosphinate)s having one, two, three or four phosphinate groups per coordination center and selected from the respective formulae: (a) MX, MaX, Ma 2  X, Ma 3  X, M(AA)X, M(AA) 2  X,   (b) MX 2 , MaX 2 , Ma 2  X 2 , MabX 2 , M(AA)X 2 ,   (c) MX 3 , MaX 3 , Ma 2  X 3 , MabX 3 , M(AA)X 3  or   (d) MX 4   wherein     M is a metal selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, titanium, zirconium, antimony, bismuth, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, cadmium, mercury, aluminum, tin, lead and mixtures thereof,   X is a disubstituted phosphinate group having the structure ##STR6##  wherein R and R 1  are independently selected from the group consisting of an aliphatic group of 1 to 20 carbons, a cycloaliphatic group of 3 to 20 carbons, an aromatic group of 6 to 12 carbons and said aliphatic, cycloaliphatic or aromatic groups can have substituted groups thereon, the substituted group being selected from the class consisting of a halogen, ether, hydroxyl, alkoxyl, ketone and ester;   a and b are independent unidentate groups selected from the class consisting of oxy, alkoxy, hydroxyl and halide; and   AA is a bidentate ligand selected from the group consisting of acetylacetonate, picolinate, 8-hydroxyquinolinate, dimethylglyoximate and glycinate.   
     
     
       7. The flame retarded compositions of claim 1 processed in the form of films, sheets, filaments, fibers and molded or extruded articles. 
     
     
       8. The flame retarded resin compositions comprising a polyester resin and a flame retardant amount, namely 2.5 to 20 parts by weight per 100 parts by weight of polyester of poly(metal phosphinate)s having two phosphinate groups per coordination center as shown in the formulae:   MX.sub.2, MaX.sub.2, Ma.sub.2 X.sub.2, MabX.sub.2, M(AA)X.sub.2     wherein   M is a metal selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, titanium, zirconium, antimony, bismuth, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, cadmium, mercury, aluminum, tin, lead and mixtures thereof,   X is a disubstituted phosphinate group having the structure ##STR7##  wherein R and R 1  are independently selected from the group consisting of an aliphatic group of 1 to 20 carbons, a cycloaliphatic group of 3 to 20 carbons, an aromatic group of 6 to 12 carbons and said aliphatic, cycloaliphatic or aromatic groups can have substituted groups thereon, the substituted group being selected from the class consisting of a halogen, ether, hydroxyl, alkoxyl, ketone and ester;   a and b are independent unidentate groups selected from the class consisting of oxy, alkoxy, hydroxyl and halide; and   AA is a bidentate ligand selected from the group consisting of acetylacetonate, picolinate, 8-hydroxyquinolinate, dimethylglyoximate and glycinate.